Adhesives and methods for their manufacture and use

ABSTRACT

A composition composed of an adhesive copolymer may be a reaction product of a first mixture and a monosaccharide monomer, in which the first mixture may be a reaction product of a diol monomer and a dicarboxylic monomer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application under 35 U.S.C. §121 ofU.S. application Ser. No. 13/520,876, filed on Jul. 6, 2012, now U.S.Pat. No. 8,937,140 and entitled “Adhesives and Methods for TheirManufacture and Use,” which is a U.S. national stage filing under 35U.S.C. §371 of International Application No. PCT/US2012/030575, filed onMar. 26, 2012, entitled “Adhesives and Methods for Their Manufacture andUse.” The disclosures of each of the foregoing are incorporated byreference in their entireties.

BACKGROUND

There is great interest in replacing petroleum-based chemicals withbio-derived feedstocks, thereby producing “green” products. Suchproducts may take advantage of renewable resources, as well as decreasemanufacturing reliance on petrochemicals. Examples of green products mayinclude inks and adhesives, including, as an example, a soy-proteinbased formaldehyde-free plywood adhesive. However, green products, ingeneral, are not well represented in the adhesives or coatings markets.

Large-scale manufacturing of bio-derived feedstocks requires asignificant market size to justify the development of biofuel processingfacilities. The combined adhesives and packaging industry is thirdbehind textiles and cosmetics. Therefore, the development of bio-derivedadhesives could greatly expand the market need for producers ofbio-derived feedstocks, such as C5 and C6 sugars.

It is therefore desirable to develop adhesive materials based on C5and/or C6 sugars to permit increased market penetration for biofuelmanufacturers.

SUMMARY

In an embodiment, a composition may be composed of an adhesive copolymerthat is a reaction product of a first mixture and a monosaccharidemonomer. The first mixture may be a reaction product of a diol monomerand a dicarboxylic monomer. Further, the dicarboxylic monomer and thediol monomer in the first mixture and the monosaccharide monomer are ata mole percent ratio of the dicarboxylic monomer to a total of themonosaccharide monomer and the diol monomer of about 85:15 to about65:35.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 a illustrates a schematic of a dicarboxylic monomer in accordancewith the present disclosure.

FIGS. 1 b and 1 c illustrate embodiments of components of a dicarboxylicmonomer in accordance with the present disclosure.

FIG. 2 illustrates an embodiment of a portion of a copolymer inaccordance with the present disclosure.

FIG. 3 illustrates another embodiment of a portion of a copolymer inaccordance with the present disclosure.

DETAILED DESCRIPTION

Carbohydrate based copolymer adhesives may be prepared from starchesderived from food grade commodities such as corn. Typically, modifiersderivable from petroleum based sources, such as formaldehyde, polyvinylalcohol, m-phenylenediamine, and triethylenetetramine, may be added.These additives may be viewed by some as potentially toxic.Additionally, production of such adhesives may still depend uponpetroleum feedstocks.

The copolymers and methods of producing them, as disclosed below, aredirected to the use of biologically derivable feedstocks, primarily C5and/or C6 monosaccharides, cross-linked by dicarboxylic monomers.Additional components, such as biologically derived diols, may be addedas chain lengthening agents to the dicarboxylic monomers. The adhesiveproperties, tensile strength, plasticity, and hardness of the copolymersmay be controlled by the ratio of dicarboxylic monomers to saccharidesin preparing the copolymers. The copolymers may also be readilybiodegradable and food safe. As such, the copolymers may be goodcandidates for use as adhesives on paper and cardboard food containers.

For the purpose of this disclosure, a “dicarboxylic monomer” may bedefined according to the structure illustrated in FIG. 1 a. Thedicarboxylic monomer 100 may comprise at least a pair of carboxyl ends,120 a and 120 b containing a carbonyl group having a carbon-oxygendouble bond. Further, the carboxyl ends may be joined by an intermediatecomponent 110. Each carboxyl end may further be conjugated to a leavinggroup, for example, the groups in FIG. 1 a designated as L₁ (to carboxylend 120 a) and L₂ (to carboxyl end 120 b). Leaving groups L₁ and L₂ mayindependently include an —O—R₁, an —S—R₂, an —NH—R₃, or an —N(R₄)(R₅)group. Leaving group L₁ may be the same type of leaving group as L₂,although the two groups may also be different types of groups ordifferent groups. It is therefore understood that a dicarboxylic monomermay comprise at least a pair of carboxyl ends, in which each carboxylend may be conjugated to a leaving group thereby forming at least one ormore of an ester, a thioester, a primary amide, or a secondary amidebond.

Groups R₁-R₅ may comprise any of a number of organic substituents,including, but not limited to, aliphatic groups and aromatic groups. Inone embodiment, either one or both of the leaving groups may include anO-aliphatic group, an O-aromatic group, an S-aliphatic group, anS-aromatic group, an N-primary amine group, or an N-secondary aminegroup. In one embodiment, the dicarboxylic monomer may be a dicarboxylicacid monomer. In one embodiment, the dicarboxylic monomer may be anα,ω-dicarboxylic acid monomer. In another embodiment, the dicarboxylicmonomer may be a dicarboxylic acid ester monomer. In yet anotherembodiment, the dicarboxylic monomer may be a dicarboxylic acid methylester monomer. In still another embodiment, the dicarboxylic monomer maybe an α,ω-dicarboxylic acid methyl ester monomer. In another embodiment,either one or both of the leaving groups may include a hydroxyl group, amethoxy group, an ethoxy group, a butoxy group, an isobutoxy group, apropoxy group, an isopropoxy group, a phenoxy group, a methyl sulfidegroup, an ethyl sulfide group, a butyl sulfide group, an isobutylsulfide group, a propyl sulfide group, an isobutyl sulfide group, aphenyl sulfide group, a methyl amine group, an ethyl amine group, abutyl amine group, an isobutyl amine group, a propyl amine group, anisopropyl amine group, an N,N-dimethyl amine group, an N,N-di-ethylamine group, an N,N-dibutyl amine group, an N,N-di-isobutyl amine group,an N,N-dipropyl amine group, or an N,N-di-isopropyl amine group.

The intermediate component of a dicarboxylic monomer may include avariety of organic groups including linear chain and branched chaingroups. In one embodiment, the intermediate component may include anunsaturated linear chain. In another embodiment, the intermediatecomponent may include a mono-unsaturated chain or a poly-unsaturatedchain. In some embodiments, the liner chain may comprise “n” carbonatoms, where “n” may be an integer from about 12 to about 34. In someembodiments, “n” may be an integer from about 16 to about 20. In stillanother embodiment, “n” may be about 18. The integer can be an evennumber or an odd number. Examples of even number include 12, 14, 16, 18,20, 22, 24, 26, 28, 30, and ranges between any two of these values.Examples of odd numbers include 13, 15, 17, 19, 21, 23, 25, 27, 29, andranges between any two of these values.

FIG. 1 b illustrates an embodiment of a poly-unsaturated linear chainintermediate component 110 of a dicarboxylic monomer that may include apropenyl repeat section within the linear chain. The propenyl moiety maybe repeated “x” times within the repeat section, where “x” may be aninteger from 0 to about 4. In some embodiments, “x” may be 0, 1, 2, 3,or 4.

The intermediate component may also include lengths of straight chainalkane moieties attached at either one or both ends of the propenylrepeat section. In one embodiment, an alkane moiety may have about 1 toabout 14 carbons. In another embodiment, an alkane moiety may have about7 to about 11 carbons. In still another embodiment, an alkane moiety mayhave about 9 carbons. Specific examples of the number of carbons include1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and ranges between anytwo of these values. It is understood that an alkane moiety attached ata first end of the propenyl repeat section may have the same number ofcarbons as an alkane moiety attached at the second end of the propenylrepeat section. Alternatively, the alkane moiety attached at a first endof the propenyl repeat section may have a different number of carbonsthan the alkane moiety attached at the second end of the propenyl repeatsection.

FIG. 1 c illustrates another embodiment of an intermediate component110. The intermediate component may include any number or distributionof unsaturated carbon-carbon double bonds along a linear chain, 130. Theintermediate component may further include one or more functional groupsincluding, without limitation, an epoxy group 150, an alcohol group 160,or a pendant vinyl group 140. The intermediate component of adicarboxylic monomer may include any or all of these groups, or otherfunctional groups.

It may be appreciated that the stereo-isomeric configuration about anyone of the carbon-carbon double bonds of a dicarboxylic monomer may havea cis configuration or a trans configuration (or alternatively stated,E- or Z-configuration). A poly-unsaturated dicarboxylic monomer mayinclude cis isomers at all carbon-carbon double bonds, trans isomers atall carbon-carbon double bonds, or a combination of cis isomers at somecarbon-carbon double bonds and trans isomers at the other carbon-carbondouble bonds.

In anticipation of material disclosed below, it may be appreciated that,while “a dicarboxylic monomer” may be disclosed, the dicarboxylicmonomer may comprise a mixture of dicarboxylic monomers as disclosedabove.

In addition to the dicarboxylic monomers, the copolymer may also beprepared using one or more monosaccharides, including pentose (C5)sugars, hexose (C6) sugars, or a combination of hexose and pentosesugars. Embodiments of monosaccharides may include, without limitation,allose, altrose, glucose, mannose, gulose, idose, galactose, talose,psicose, fructose, sorbose, tagatose, arabinose, lyxose, ribose, xylose,ribulose, or xylulose. In anticipation of material disclosed below, itmay be appreciated that, while “a monosaccharide monomer” may bedisclosed, the monosaccharide monomer may comprise a mixture ofmonosaccharide monomers.

Further, the copolymer may also be prepared using one or more diolmonomers, including, without limitation, octane-1,3-diol,cis-oct-5-ene-1,3-diol, isosorbide, 1,3-propanediol, 1,2-propanediol,and 1,4-butanediol.

FIG. 2 illustrates an embodiment of a portion 200 of the copolymer. Thecopolymer comprises at least one monosaccharide moiety partiallycross-linked to a dicarboxylic moiety. FIG. 2 illustrates a number ofmonosaccharide moieties, 220, 225, and 230, cross-linked to a number ofdicarboxylic moieties, such as 210. The degree of cross-linking may bevariable. Thus, monosaccharide moiety 225 is cross-linked to a singledicarboxylic moiety at one carboxyl end. Monosaccharide moiety 220 iscross-linked to two separate dicarboxylic moieties; monosaccharidemoiety 230 is cross-linked to three separate dicarboxylic moieties. Itis possible to describe the copolymer in terms of an average number ofdicarboxylic moieties cross-linked to a single monosaccharide moiety. InFIG. 2, monosaccharide moiety 225 is cross-linked to a singledicarboxylic moiety, monosaccharide moiety 220 is cross-linked to two,and monosaccharide moiety 230 is cross-linked to three dicarboxylicmoieties. Thus, for the portion of the copolymer illustrated in FIG. 2,the average number of dicarboxylic moieties cross-linked to a singlemonosaccharide moiety is 2. In some embodiments, the averagecross-linking number may be from about 1.2 to about 3.2 In otherembodiments, the average cross-linking number may be from about 2.0 toabout 2.6. Specific examples of the average cross-linked number include1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, 2.6, 2.8, 3.0, 3.2, and rangesbetween any two of these values.

It is apparent in FIG. 2 that the cross-linking is accomplished throughester bonds formed by a carboxyl end of a dicarboxylic moiety and ahydroxyl function of a monosaccharide moiety. A dicarboxylic moiety 210may be cross-linked to one monosaccharide moiety at one carboxyl end,and cross-linked to a second monosaccharide moiety at the secondcarboxyl end. Alternatively, a dicarboxylic moiety may be cross-linkedto a single monosaccharide at one carboxyl end, and cross-linked to agroup L₁ at the second carboxyl end 235. In some embodiments, L₁ maycomprise a leaving group associated with a precursor dicarboxylicmonomer. Group L₁ may include, without limitation, an O-aliphatic group,an O-aromatic group, an S-aliphatic group, an S-aromatic group, anN-primary amine group, or an N-secondary amine group. In someembodiments, group L₁ may include, without limitation, a hydroxyl group,a methoxy group, an ethoxy group, a butoxy group, an isobutoxy group, apropoxy group, an isopropoxy group, a phenoxy group, a methyl sulfidegroup, an ethyl sulfide group, a butyl sulfide group, an isobutylsulfide group, a propyl sulfide group, an isobutyl sulfide group, aphenyl sulfide group, a methyl amine group, an ethyl amine group, abutyl amine group, an isobutyl amine group, a propyl amine group, anisopropyl amine group, an N,N-dimethyl amine group, an N,N-di-ethylamine group, an N,N-dibutyl amine group, an N,N-di-isobutyl amine group,an N,N-dipropyl amine group, or an N,N-di-isopropyl amine group. Thus,in some embodiments, a group L₁ or L₂ conjugated to a precursordicarboxylic monomer may become incorporated into the copolymer.

FIG. 3 illustrates a portion of another embodiment of the copolymer. Inparticular, FIG. 3 illustrates a portion of a copolymer 300 that may beprepared from dicarboxylic monomers, monosaccharide monomers, and diolmonomers. In addition to monosaccharide moieties such as 330, thecopolymer may further comprise dicarboxylic moieties such as 310, 325,and 320. FIG. 3 illustrates, for example, a dicarboxylic moietycross-linked to a first monosaccharide moiety at a first carboxyl end,and cross-linked to a second monosaccharide moiety at the secondcarboxyl end. FIG. 3 further illustrates a dicarboxylic moietycross-linked to a monosaccharide 330 at one carboxyl end andcross-linked to a non-monosaccharide moiety L₁ at a second carboxyl end.Additionally, a dicarboxylic moiety may be cross-linked to a diolmoiety, such as 310, 320, and 325. A diol moiety 315 may be cross-linkedto one dicarboxylic moiety 310 at a first hydroxyl group, andcross-linked to a second dicarboxyl moiety 325 at the second hydroxylgroup. Alternatively, a diol moiety 340 may be cross-linked to only onedicarboxylic moiety 320.

In one embodiment, the copolymer may be prepared as a reaction productof monosaccharide monomers and dicarboxylic monomers in the presence ofat least one catalyst within a mixture. Under suitable conditions, acopolymer with adhesive properties may be produced.

In one embodiment, the monosaccharide monomers may include one or moremonosaccharides, including pentose (C5) sugars, hexose (C6) sugars, or acombination of hexose and pentose sugars. Embodiments of monosaccharidesmay include, without limitation, allose, altrose, glucose, mannose,gulose, idose, galactose, talose, psicose, fructose, sorbose, tagatose,arabinose, lyxose, ribose, xylose, ribulose, or xylulose. It may beappreciated that the monosaccharide monomers may comprise a single typeof monosaccharide or a mixture of monosaccharides.

In one embodiment, the dicarboxylic monomers may include one or moredicarboxylic monomers comprising at least a pair of carboxyl ends, eachcarboxyl end containing a carbonyl carbon-oxygen double bond, in whichthe carboxyl ends may be joined by an intermediate component. Eachcarboxyl end may further be conjugated to a leaving group, which may,independently, include an —O—R₁, an —S—R₂, an —NH—R₃, or an —N(R₄)(R₅)group. The leaving groups associated with the carboxyl ends may comprisethe same type of leaving group, or they may differ.

Groups R₁-R₅ may comprise any of a number of organic substituents,including, but not limited to, aliphatic groups and aromatic groups. Inone embodiment, either one or both of the leaving groups may include anO-aliphatic group, an O-aromatic group, an S-aliphatic group, anS-aromatic group, an N-primary amine group, or an N-secondary aminegroup. In one embodiment, the dicarboxylic monomer may be a dicarboxylicacid monomer. In one embodiment, the dicarboxylic monomer may be anα,ω-dicarboxylic acid monomer. In another embodiment, the dicarboxylicmonomer may be a dicarboxylic acid ester monomer. In yet anotherembodiment, the dicarboxylic monomer may be a dicarboxylic acid methylester monomer. In still another embodiment, the dicarboxylic monomer maybe an α,ω-dicarboxylic acid methyl ester monomer. In another embodiment,either one or both of the leaving groups may include a hydroxyl group, amethoxy group, an ethoxy group, a butoxy group, an isobutoxy group, apropoxy group, an isopropoxy group, a phenoxy group, a methyl sulfidegroup, an ethyl sulfide group, a butyl sulfide group, an isobutylsulfide group, a propyl sulfide group, an isobutyl sulfide group, aphenyl sulfide group, a methyl amine group, an ethyl amine group, abutyl amine group, an isobutyl amine group, a propyl amine group, anisopropyl amine group, an N,N-dimethyl amine group, an N,N-di-ethylamine group, an N,N-dibutyl amine group, an N,N-di-isobutyl amine group,an N,N-dipropyl amine group, or an N,N-di-isopropyl amine group.

The intermediate components of the dicarboxylic monomers may include avariety of organic groups including linear chain and branched chaingroups. In one embodiment, the intermediate group may include anunsaturated linear chain. In another embodiment, the intermediate groupmay include a mono-unsaturated chain or a poly-unsaturated chain. Insome embodiments, the liner chain may comprise “n” carbon atoms, where“n” may be an integer from about 12 to about 34. In some embodiments,“n” may be an integer from about 16 to about 20. In still anotherembodiment, “n” may be about 18. The integer can be an even number or anodd number. Examples of even number include 12, 14, 16, 18, 20, 22, 24,26, 28, 30, and ranges between any two of these values. Examples of oddnumbers include 13, 15, 17, 19, 21, 23, 25, 27, 29, and ranges betweenany two of these values.

In one embodiment, the intermediate group may comprise apoly-unsaturated linear chain including a propenyl repeat section. Thepropenyl moiety may be repeated “x” times within the repeat section,where “x” may be an integer from 0 to about 4. In some embodiments, “x”may be 0, 1, 2, 3, or 4.

The intermediate component may also include lengths of straight chainalkane moieties attached at either one or both ends of the propenylrepeat section. In one embodiment, an alkane moiety may have about 1 toabout 14 carbons. In another embodiment, an alkane moiety may have about7 to about 11 carbons. In still another embodiment, an alkane moiety mayhave about 9 carbons. Specific examples of the number of carbons include1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and ranges between anytwo of these values. It is understood that an alkane moiety attached ata first end of the propenyl repeat section may have the same number ofcarbons as an alkane moiety attached at the second end of the propenylrepeat section. Alternatively, the alkane moiety attached at a first endof the propenyl repeat section may have a different number of carbonsthan the alkane moiety attached at the second end of the propenyl repeatsection.

In another embodiment, the intermediate component may include any numberor distribution of unsaturated carbon-carbon double bonds along a linearchain. The intermediate component may further include one or morefunctional groups including, without limitation, an epoxy group, analcohol group, or a pendant vinyl group. The intermediate components ofthe dicarboxylic monomers may include any or all of these groups, orother functional groups.

It may be appreciated that the stereo-isomeric configuration about anyone of the carbon-carbon double bonds of a dicarboxylic monomer may havea cis configuration or a trans configuration (or alternatively stated,E- or Z-configuration). A poly-unsaturated dicarboxylic monomer mayinclude cis isomers at all carbon-carbon double bonds, trans isomers atall carbon-carbon double bonds, or a combination of cis isomers at somecarbon-carbon double bonds and trans isomers at the other carbon-carbondouble bonds.

It may be appreciated that the dicarboxylic monomers may comprise asingle type of dicarboxylic monomer or a mixture of dicarboxylicmonomers.

In one embodiment, the dicarboxylic monomers and the monosaccharidemonomers may be present initially in the mixture at a mole percent ratioof about 85:15 to about 65:35. In one embodiment, the dicarboxylicmonomers and the monosaccharide monomers may be present initially in themixture at a mole percent ratio of about 80:20 to about 70:30. Specificexamples of the mole percent ratio include 80:20, 75:25, 70:30, 65:35,and ranges between any two of these values.

At least one catalyst may be used in the preparation of the copolymer.In one embodiment, the catalyst may comprise a strong Lewis acid. Asnon-limiting examples, the strong Lewis acid may comprise any one ormore of hydrochloric acid, phosphoric acid, nitric acid, or sulfuricacid. In one embodiment, the catalyst may comprise phosphoric acid. Inanother embodiment, the catalyst may comprise a coordinating compound.Non-limiting examples of such coordinating compounds may include one ormore of a first row transition metal halide, a second row transitionmetal halide, a third row transition metal halide, a lanthanide salt, orany combination thereof. In one embodiment, the coordinating compoundmay comprise ferric chloride. In another embodiment, the catalyst maycomprise a combination of a strong Lewis acid and a coordinatingcompound. As one example, the catalyst may comprise both phosphoric acidand ferric chloride.

In one embodiment, the catalyst and the dicarboxylic monomers and may bepresent initially in the mixture at a weight ratio of about 1:1 to about1:200. Specific examples of the initial weight ratio include, 1:1, 1:2,1:5, 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:120, 1:140, 1:160, 1:180,1:200, and ranges between any two of these values. In one embodiment, astrong Lewis acid catalyst and the dicarboxylic monomers may be presentinitially in the mixture at a weight ratio of about 1:2. In anotherembodiment, a coordinating compound catalyst and the dicarboxylicmonomers may be present initially in the mixture at a weight ratio ofabout 1:10.

In one embodiment of a method of preparing the copolymer, themonosaccharide monomers, the dicarboxylic monomers, and catalyst may bepresent as a mixture in one or more mixing vessels. In an embodiment,the mixture may be mixed under suitable conditions. In anotherembodiment, the mixture may be stirred continuously. In still anotherembodiment, the mixture may be shaken within the one or more vessels.Alternative methods to combine and contact the components of the mixturemay also be anticipated by this disclosure.

Under suitable conditions, a copolymer with adhesive properties may beproduced as a reaction product of the mixture of monosaccharidemonomers, dicarboxylic monomers, and catalyst. Suitable conditions mayinclude heating the mixture at a specified temperature for a specifiedperiod of time. In one embodiment, the mixture may be heated at a firsttemperature of about 60° C. to about 180° C. In one embodiment, themixture may be heated at a first temperature of about 80° C. to about160° C. Specific examples of the first temperature include, 60° C., 80°C., 100° C., 120° C., 140° C., 150° C., 160° C., 180° C., and rangesbetween any two of these values. In still another embodiment, themixture may be heated at a first temperature of about 150° C. In anembodiment, the mixture may be heated at a first temperature for aperiod of time of about 1 hour to about 12 hours. In another embodiment,the mixture may be heated at a first temperature for a period of time ofabout 1.5 hours to about 10 hours. Specific examples of the period oftime include, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6hours, 8 hours, 10 hours, 12 hours, and ranges between any two of thesevalues. In yet another embodiment, the mixture may be heated at a firsttemperature for about 2 hours.

Suitable conditions may further include heating the mixture at a secondspecified temperature for a second specified period of time. In oneembodiment, the mixture may be heated at a second temperature of about150° C. to about 220° C. In one embodiment, the mixture may be heated ata second temperature of about 160° C. to about 210° C. Specific examplesof the second temperature include 150° C., 160° C., 170° C., 180° C.,190° C., 200° C., 210° C., and ranges between any two of these values.In still another embodiment, the mixture may be heated at a secondtemperature of about 200° C. In an embodiment, the mixture may be heatedat a second temperature for a period of time of about 1 minute to about60 minutes. In another embodiment, the mixture may be heated at a secondtemperature for a period of time of about 3 minutes to about 30 minutes.Specific examples of a period of time include 1 minute, 2 minutes, 3minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 40minutes, 45 minutes, 50 minutes, 60 minutes, and ranges between any twoof these values. In yet another embodiment, the mixture may be heated ata second temperature for about 5 minutes.

In another embodiment, the copolymer may be prepared as a reactionproduct of diol monomers, dicarboxylic monomers, and monosaccharidemonomers. A first mixture may be prepared by contacting the diolmonomers and dicarboxylic monomers in the presence of at least onecatalyst. The first mixture may then be placed under a first set ofconditions. Thereafter, the first mixture may be contacted withmonosaccharide monomers to form a second mixture. Under a suitable setof second conditions, a copolymer with adhesive properties may beproduced from the second mixture.

In one embodiment, the monosaccharide monomers may include one or moremonosaccharides, including pentose (C5) sugars, hexose (C6) sugars, or acombination of hexose and pentose sugars. Embodiments of monosaccharidesmay include, without limitation, substantially the group ofmonosaccharides as disclosed above. It may be appreciated that themonosaccharide monomers may comprise a single type of monosaccharide ora mixture of monosaccharides.

In one embodiment, the dicarboxylic monomers may include one or moredicarboxylic monomers comprising at least a pair of carboxyl ends, eachcarboxyl end containing a carbonyl carbon-oxygen double bond, in whichthe carboxyl ends may be joined by an intermediate component.Embodiments of the intermediate components may include, withoutlimitation, the group of intermediate components as substantiallydisclosed above. Each carboxyl end may further be conjugated to aleaving group, which may include an —O—R₁, an —S—R₂, an —NH—R₃, or an—N(R₄)(R₅) group. The leaving groups associated with the carboxyl endsmay comprise the same type of leaving group, or they may differ.Embodiments of groups R₁-R₅ may include, without limitation, the groupsof R₁-R₅ as substantially disclosed above.

In one embodiment, the diol monomers may include, without limitation,octane-1,3-diol, cis-oct-5-ene-1,3-diol, isosorbide, 1,3-propanediol,1,2-propanediol, and 1,4-butanediol.

At least one catalyst may be used in the preparation of the copolymer.Embodiments of catalysts may include, without limitation, the groups ofcatalysts as substantially disclosed above.

In one embodiment, the dicarboxylic monomers and the diol monomers maybe present initially in the first mixture at a mole percent ratio ofabout 85:3 to about 65:30. In one embodiment, the dicarboxylic monomersand the diol monomers may be present initially in the first mixture at amole percent ratio of about 85:3 to about 85:12. In another embodiment,the dicarboxylic monomers and the diol monomers may be present initiallyin the first mixture at a mole percent ratio of about 65:5 to about65:30. Specific examples of a mole percent ratio include 85:5, 85:7,85:9, 85:10, 65:5, 65:10, 65:15, 65:20, 65:25, 80:4, 80:8, 80:12, 80:16,75:5, 75:10, 75:15, 75:21, 70:5, 70:10, 70:15, 70:20, 70:25, and rangesbetween any two of these values. In yet another embodiment, thedicarboxylic monomers and the diol monomers may be present initially ina first mixture at a mole percent ratio of about 75:4.

In one embodiment, the catalyst and the dicarboxylic monomers and may bepresent initially in the first mixture at a weight ratio of about 1:1 toabout 1:200. Specific examples of the initial weight ratio include 1:1,1:2, 1:5, 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:120, 1:140, 1:160,1:180, 1:200, and ranges between any two of these values. In oneembodiment, a strong Lewis acid catalyst and the dicarboxylic monomersmay be present initially in the first mixture at a weight ratio of about1:2. In another embodiment, a coordinating compound catalyst and thedicarboxylic monomers may be present initially in the first mixture at aweight ratio of about 1:10.

During the preparation of the copolymer, the diol monomers, thedicarboxylic monomers, and catalyst may be present as a first mixture inone or more mixing vessels. In an embodiment, the first mixture may bemixed under suitable conditions. In another embodiment, the firstmixture may be stirred continuously. In still another embodiment, thefirst mixture may be shaken within the one or more vessels. Alternativemethods to combine and contact the components of the first mixture mayalso be anticipated by this disclosure.

The first mixture may be exposed to a first set of conditions. The firstset of conditions may include heating the first mixture at least at afirst specified temperature for a first specified period of time. In oneembodiment, the first mixture may be heated at a temperature of about60° C. to about 180° C. In one embodiment, the first mixture may beheated at a temperature of about 80° C. to about 160° C. Specificexamples of the first temperature include, 60° C., 80° C., 100° C., 120°C., 140° C., 150° C., 160° C., 180° C., and ranges between any two ofthese values. In still another embodiment, the first mixture may beheated at a temperature of about 150° C. In an embodiment, the firstmixture may be heated for a period of time of about 1 hour to about 12hours. In another embodiment, the first mixture may be heated for aperiod of time of about 1.5 hours to about 10 hours. Specific examplesof the period of time include 1 hour, 1.5 hours, 2 hours, 3 hours, 4hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, and ranges betweenany two of these values. In yet another embodiment, the first mixturemay be heated for about 2 hours.

The first mixture may then be contacted with monosaccharide monomers toform a second mixture. In an embodiment, the second mixture may be mixedunder suitable conditions. In another embodiment, the second mixture maybe stirred continuously. In still another embodiment, the second mixturemay be shaken within one or more vessels. It is understood that thevessel or vessels containing the second mixture may be the same vesselor vessels that contained the first mixture. Alternatively, the secondmixture may be contained in one or more additional or alternativevessels. Alternative methods to combine and contact the components ofthe second mixture may also be anticipated by this disclosure.

In one embodiment, the dicarboxylic monomers and the diol monomerspresent initially in the first mixture, and the monosaccharide monomerspresent initially in the second mixture may be present at a mole percentratio of dicarboxylic monomer to the total of the monosaccharide monomerplus diol monomer from about 85:15 to about 65:35. In one embodiment,the dicarboxylic monomers and the diol monomers present initially in thefirst mixture, and the monosaccharide monomers present initially in thesecond mixture may be present at a mole percent ratio of dicarboxylicmonomer to the total of the monosaccharide monomer plus diol monomerfrom about 80:20 to about 70:30. Specific examples of the mole percentratio of dicarboxylic monomer to the total of the monosaccharide monomerplus diol monomer include 80:20, 75:25, 70:30, 65:35, and ranges betweenany two of these values. In yet another embodiment, the dicarboxylicmonomers and the diol monomers present initially in the first mixture,and the monosaccharide monomers present initially in the second mixturemay be present at a mole percent ratio of dicarboxylic monomer to thetotal of the monosaccharide monomer plus diol monomer from about 75:25.

Under suitable conditions, a copolymer with adhesive properties may beproduced as a reaction product of the second mixture. Suitableconditions may include heating the second mixture at a specifiedtemperature for a specified period of time. In one embodiment, thesecond mixture may be heated at a first temperature of about 60° C. toabout 180° C. In one embodiment, the second mixture may be heated at afirst temperature of about 80° C. to about 160° C. Specific examples ofthe first temperature include 60° C., 80° C., 100° C., 120° C., 140° C.,150° C., 160° C., 180° C., and ranges between any two of these values.In still another embodiment, the second mixture may be heated at a firsttemperature of about 150° C. In an embodiment, the second mixture may beheated at a first temperature for a period of time of about 1 hour toabout 12 hours. In another embodiment, the second mixture may be heatedat a first temperature for a period of time of about 1.5 hours to about10 hours. Specific examples of the period of time include 1 hour, 1.5hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours,12 hours, and ranges between any two of these values. In yet anotherembodiment, the mixture may be heated at a first temperature for about 2hours.

Suitable conditions may further include heating the second mixture at asecond specified temperature for a second specified period of time. Inone embodiment, the second mixture may be heated at a second temperatureof about 150° C. to about 220° C. In one embodiment, the second mixturemay be heated at a second temperature of about 160° C. to about 210° C.Specific examples of the second temperature include 150° C., 160° C.,170° C., 180° C., 190° C., 200° C., 210° C., and ranges between any twoof these values. In still another embodiment, the second mixture may beheated at a second temperature of about 200° C. In an embodiment, thesecond mixture may be heated at a second temperature for a period oftime of about 1 minute to about 60 minutes. In another embodiment, thesecond mixture may be heated at a second temperature for a period oftime of about 3 minutes to about 30 minutes. Specific examples of aperiod of time include 1 minute, 2 minutes, 3 minutes, 5 minutes, 10minutes, 15 minutes, 20 minutes, 30 minutes, 40 minutes, 45 minutes, 50minutes, 60 minutes, and ranges between any two of these values. In yetanother embodiment, the second mixture may be heated at a secondtemperature for about 5 minutes.

EXAMPLES Example 1 A Copolymer Adhesive Material

A copolymer adhesive material may be prepared by mixing about 84 gramsof a mixture of C5/C6 monosaccharides comprising about 26.4% arabinose,about 50.4% galactose, about 15.6% xylose, and about 7.6% glucose(monosaccharide monomers), 10 grams of α,ω-(9Z)-octadec-9-enedioic aciddimethyl ester (dicarboxylic monomer), 5 grams of phosphoric acid(strong Lewis acid catalyst), and 1 gram of ferric chloride(coordinating compound catalyst) in an oil-jacketed stainless steelsigma-blade mixer. The mixture may be continuously stirred while heatedat about 150° C. for about 2 hours. Thereafter, the mixture may beheated to at least 200° C. for about 2 minutes. The resulting copolymermaterial may be a dry amorphous solid similar to common poly-vinylacetate-based glues. The adhesive material may have a melting point ofabout −15° C. and a tensile strength of about 380 psi (2.62 MPa).

Example 2 A Method of Preparing a First Copolymer Adhesive Material

To an oil jacketed stainless steel sigma-blade mixer may be added about84 grams of a mixture of C5/C6 monosaccharides comprising about 26.4%arabinose, about 50.4% galactose, about 15.6% xylose, and about 7.6%glucose (monosaccharide monomer), 10 grams ofα,ω-(9Z)-octadec-9-enedioic acid dimethyl ester (dicarboxylic monomer),5 grams of phosphoric acid (strong Lewis acid catalyst), and 1 gram offerric chloride (coordinating compound catalyst). The mixture may becontinuously stirred while heated at about 150° C. for about 2 hours.Thereafter, the mixture may be heated to at least 200° C. for about 2minutes.

Example 3 A Method of Preparing a Second Copolymer Adhesive Material

To an oil jacketed stainless steel sigma-blade mixer may be added 4.3grams of isosorbide (diol monomer), 10 grams ofα,ω-(9Z)-octadec-9-enedioic acid dimethyl ester (dicarboxylic monomer),5 grams of phosphoric acid (strong Lewis acid catalyst), and 1 gram offerric chloride (coordinating compound catalyst) to form a firstmixture. The first mixture may be continuously stirred while heated atabout 150° C. for about 2 hours. Thereafter, 79.7 grams of a mixture ofC5/C6 monosaccharides comprising about 26.4% arabinose, about 50.4%galactose, about 15.6% xylose, and about 7.6% glucose (monosaccharidemonomer) may be added to the first mixture, thereby creating a secondmixture. The second mixture may then be heated for another 2 hours at150° C. under continuous stirring. After this first period of time, themixture may be heated further to at least 200° C. for about 2 minutes.

Example 4 Use of a Copolymer Adhesive Material for Binding WoodPulp-Based Products

One piece of a wood pulp-based product, such as bond paper, cardboard,or fiberboard, may be coated on one side with a thin layer of acopolymer adhesive. A second piece a wood pulp-based product may bepressed against the layer of adhesive and held in fixed position untilthe adhesive dries at ambient temperature, about 68° F. (20° C.) toabout 79° F. (26° C.). It is understood that the two pieces of woodpulp-based material may be the same or may differ. The dried copolymeradhesive may have a lap shear strength of about 400 psi (2.76 MPa).Compared to other common adhesives, the copolymer adhesive disclosedabove may be produced entirely from renewable resources, and may notrequire feedstocks from petrochemical sources.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated in this disclosure, will be apparent to those skilled in theart from the foregoing descriptions. Such modifications and variationsare intended to fall within the scope of the appended claims. Thepresent disclosure is to be limited only by the terms of the appendedclaims, along with the full scope of equivalents to which such claimsare entitled. It is to be understood that this disclosure is not limitedto particular methods, reagents, compounds, or compositions, which can,of course, vary. It is also to be understood that the terminology usedin this disclosure is for the purpose of describing particularembodiments only, and is not intended to be limiting.

With respect to the use of substantially any plural and/or singularterms in this disclosure, those having skill in the art can translatefrom the plural to the singular and/or from the singular to the pluralas is appropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth in thisdisclosure for sake of clarity. It will be understood by those withinthe art that, in general, terms used in this disclosure, and especiallyin the appended claims (e.g., bodies of the appended claims) aregenerally intended as “open” terms (e.g., the term “including” should beinterpreted as “including but not limited to,” the term “having” shouldbe interpreted as “having at least,” the term “includes” should beinterpreted as “includes but is not limited to,” etc.). While variouscompositions, methods, and devices are described in terms of“comprising” various components or steps (interpreted as meaning“including, but not limited to”), the compositions, methods, and devicescan also “consist essentially of” or “consist of” the various componentsand steps, and such terminology should be interpreted as definingessentially closed-member groups.

It will be further understood by those within the art that if a specificnumber of an introduced claim recitation is intended, such an intentwill be explicitly recited in the claim, and in the absence of suchrecitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). It will be further understood by those within the artthat virtually any disjunctive word and/or phrase presenting two or morealternative terms, whether in the description, claims, or drawings,should be understood to contemplate the possibilities of including oneof the terms, either of the terms, or both terms. For example, thephrase “A or B” will be understood to include the possibilities of “A”or “B” or “A and B.”

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed in this disclosure also encompass any and all possiblesubranges and combinations of subranges thereof. Any listed range can beeasily recognized as sufficiently describing and enabling the same rangebeing broken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed in thisdisclosure can be readily broken down into a lower third, middle thirdand upper third, etc. As will also be understood by one skilled in theart all language such as “up to,” “at least,” and the like include thenumber recited and refer to ranges which can be subsequently broken downinto subranges as discussed above. Finally, as will be understood by oneskilled in the art, a range includes each individual member.

From the foregoing, it will be appreciated that various embodiments ofthe present disclosure have been described for purposes of illustration,and that various modifications may be made without departing from thescope and spirit of the present disclosure. Accordingly, the variousembodiments disclosed are not intended to be limiting, with the truescope and spirit being indicated by the following claims.

What is claimed is:
 1. A composition comprising an adhesive copolymer,wherein the adhesive copolymer is a reaction product of a first mixtureand a monosaccharide monomer, wherein the first mixture is a reactionproduct of a diol monomer and a dicarboxylic monomer, wherein thedicarboxylic monomer and the diol monomer in the first mixture and themonosaccharide monomer are at a mole percent ratio of the dicarboxylicmonomer to a total of the monosaccharide monomer and the diol monomer ofabout 85:15 to about 65:35, and wherein the adhesive copolymer comprisesat least one dicarboxyl moiety including an epoxy group.
 2. Thecomposition of claim 1, wherein the monosaccharide monomer is a pentose(C5) sugar, a hexose (C6) sugar, or a combination thereof.
 3. Thecomposition of claim 1, wherein the monosaccharide monomer comprises oneor more of the following: allose, altrose, glucose, mannose, gulose,idose, galactose, talose, psicose, fructose, sorbose, tagatose,arabinose, lyxose, ribose, xylose, ribulose, and xylulose.
 4. Thecomposition of claim 1, wherein the dicarboxylic monomer is adicarboxylic acid monomer.
 5. The composition of claim 1, wherein thedicarboxylic monomer is an α,ω-dicarboxylic acid monomer.
 6. Thecomposition of claim 1, wherein the dicarboxylic monomer is adicarboxylic acid ester monomer.
 7. The composition of claim 1, whereinthe dicarboxylic monomer is a dicarboxylic acid methyl ester monomer. 8.The composition of claim 1, wherein the dicarboxylic monomer is anα,ω-dicarboxylic acid methyl ester monomer.
 9. The composition of claim1, wherein the dicarboxylic monomer comprises one or more of thefollowing: a dicarboxylic dimethyl ester, a dicarboxylic di-ethyl ester,a dicarboxylic dipropyl ester, a dicarboxylic di-isopropyl ester, adicarboxylic dibutyl ester, a dicarboxylic di-isobutyl ester, adicarboxylic methyl-ethyl ester, a dicarboxylic methyl-propyl ester, adicarboxylic methyl-isopropyl ester, a dicarboxylic methyl-butyl ester,a dicarboxylic methyl-isobutyl ester, a dicarboxylic ethyl-propyl ester,a dicarboxylic ethyl-isopropyl ester, a dicarboxylic ethyl-butyl ester,a dicarboxylic ethyl-isobutyl ester, a dicarboxylic propyl-isopropylester, a dicarboxylic propyl-butyl ester, a dicarboxylic propyl-isobutylester, a dicarboxylic isopropyl-butyl ester, a dicarboxylicisopropyl-isobutyl ester, and a dicarboxylic butyl-isobutyl ester. 10.The composition of claim 1, wherein the dicarboxylic monomer comprises alinear chain of “n” carbon atoms, where “n” is an integer of about 12 toabout
 34. 11. The composition of claim 1, wherein the dicarboxylicmonomer comprises a linear chain of “n” carbon atoms, where “n” is aninteger of about 16 to about
 20. 12. The composition of claim 1, whereinthe dicarboxylic monomer comprises a linear chain of “n” carbon atoms,where “n” is
 18. 13. The composition of claim 1, wherein the adhesivecopolymer comprises at least one monosaccharide moiety crosslinked to aplurality of dicarboxyl moieties.
 14. The composition of claim 1 whereinthe adhesive copolymer comprises at least one dicarboxyl moietycross-linked at a first carboxyl end to a first monosaccharide moietyand at a second carboxyl end to a second monosaccharide moiety.
 15. Thecomposition of claim 1, wherein the adhesive copolymer comprises atleast one dicarboxyl moiety cross-linked at a carboxyl end to one of thefollowing groups: an O-aliphatic group, an O-aromatic group, anS-aliphatic group, an S-aromatic group, an N-primary amine, and anN-secondary amine.
 16. The composition of claim 1, wherein the adhesivecopolymer comprises at least one dicarboxyl moiety cross-linked at acarboxyl end to one of the following: a methoxy group, an ethoxy group,a butoxy group, an isobutoxy group, a propoxy group, an isopropoxygroup, a phenoxy group, a methyl sulfide group, an ethyl sulfide group,a butyl sulfide group, an isobutyl sulfide group, a propyl sulfidegroup, an isobutyl sulfide group, a phenyl sulfide group, a methyl aminegroup, an ethyl amine group, a butyl amine group, an isobutyl aminegroup, a propyl amine group, an isopropyl amine group, an N,N-dimethylamine group, an N,N-di-ethyl amine group, an N,N-dibutyl amine group, anN,N-di-isobutyl amine group, an N,N-dipropyl amine group, and anN,N-di-isopropyl amine group.
 17. The composition of claim 1, whereinthe adhesive copolymer comprises at least a first dicarboxyl moietycross-linked at a first carboxyl end to a first hydroxyl group of a diolmoiety, and at least a second dicarboxyl moiety cross-linked at a firstcarboxyl end to a second hydroxyl group of the diol moiety.
 18. Thecomposition of claim 17, wherein the diol moiety comprises one or moreof the following: an octane-1,3-diol moiety, a cis-oct-5-ene-1,3-diolmoiety, an isosorbide moiety, a 1,3-propanediol moiety, a1,2-propanediol moiety, and a 1,4-butanediol moiety.
 19. The compositionof claim 1, wherein the adhesive copolymer comprises about 1.2 to about3.2 dicarboxyl moieties cross-linked to a single monosaccharide moiety.20. The composition of claim 1, wherein the adhesive copolymer comprisesabout 2.0 to about 2.6 dicarboxyl moieties cross-linked to a singlemonosaccharide moiety.
 21. The composition of claim 1, wherein theadhesive copolymer comprises 2.5 dicarboxyl moieties cross-linked to asingle monosaccharide moiety.